Processes for repelling insects by means of N-alkyl neoalkanamide insect repellents

ABSTRACT

N-lower alkyl neoalkanamides (N-lower alkyl trialkylacetamides of certain types) of 1 to 4 carbon atoms in the lower alkyl thereof and of 5 to 14 carbon atoms in the neoalkanoyl (or trialkylacetyl) group, e.g., N-methyl- and N-ethyl neodecanamides and N-methyl and N-ethyl neotridecanamides, are new componds, secondary amides which have insect repellent properties, being especially effective against cockroaches, e.g., the German cockroach. However, they are also useful as repellents for other insects, including American cockroaches, mosquitoes, flies, fleas, ants, and lice. Additionally, they may repel arachnids, such as spiders, ticks and mites. The new neoalkanamides may be synthesized easily, as by reacting a primary lower alkyl amine with a neoalkanoyl halide, e.g. by reacting methyl amine or ethyl amine with neodecanoyl chloride. 
     The most effective of the described amides for insect repellency are normally liquid and are sufficiently volatile to be detectable in air by insects. They have been found to be of long lasting effectiveness, with significant and measurable insect repellency being obtainable for as long as two weeks after application.

This application is a continuation-in-part of my U.S. patent applicationSer. No. 06/894,985, now abandoned, and a continuation-in-part of Ser.No. 07/071,305, now U.S. Pat. No. 4,804,683.

This invention relates to N-alkyl neoalkanamides, which are novelchemical compounds that possess insect repelling properties. Morespecifically, this invention relates to N-lower alkyl neoalkanamides.The mentioned neoalkanamides especially N-methyl and N-ethylneodecanamides, have been found to be especially effective in repellinginsects, such as German cockroaches, when applied to surfaces ofstructures, items and materials to be protected. The present inventionalso relates to various compositions containing such N-alkylneoalkanamides, which compositions are employed as means for depositingsuch active compounds onto surfaces to be made repellent to insects.

Although some insects, such as bees, are considered to be useful to man(for plant pollination), many types of insects are classified as pests,and many efforts have been made to eradicate or at least control them.However, although effective poisons have been produced, various insectshave developed resistances to them (possibly by "natural selection") andothers have been able to detect and avoid poisons. Furthermore, manypoisons have undesirable effects on human and other animal life, andtherefore use thereof has often been regulates or forbidden. Someinsects, like the common German or house cockroach, cannot be eliminatedentirely from many areas and therefore, realistically, efforts have beenmade to control them rather than to eradicate them. Mosquito repellentshave long been marketed and some chemicals that are effective inrepelling roaches have been discovered. Such chemicals may be applied tosurfaces of walls, floors, carbinets, drawers, packages, containers,rugs, upholstery and carpeting, and in potential nesting places forinsects, such as inside walls and between floors. Similarly, when suchrepellents are of low toxicity they may be applied to the human body andonto pets, zoo animals and livestock. However, some such repellentmaterials are toxic and others are foul smelling and discoloring, whichadverse properties can seriously limit their utilities. Most of theuseful insect repellents reported in the literature are tertiary amidesand of these the one heretofore regarded as the most effectiveall-purpose insect repellent is N,N-diethyl-m-toluamide, which is oftenreferred to as "DEET". However, the present neoalkanamides, and N-methylneodecanamide in particular, are superior to DEET in long lastingeffectiveness and in at least one entomological laboratory, havereplaced DEET as the standard of repellent action (against roaches).Additionally, such neoalkanamide is also effective to repel otherinsects, including mosquitoes, and has been found to be of greatereffectiveness against Anopheles quadrimaculatus than DEET. In view ofthe relatively small number of useful insect repellents known, effortscontinue to be made to discover additional repellents which would be ofgreater repellent actions and of longer lasting effects. Desirably, suchcompounds also would be of improved physical characteristics, such as ofmore pleasant aroma, desirable volatility, non-staining character,liquid state (preferable), improved stability, greater substantivity tosubstrates, and longer lasting repellent effect.

In accordance with the present invention N-alkyl neoalkanamides that areintended for use as insect repellents have been discovered in which thealkyl thereof is of 1 to 18, preferably 1 to 4 carbon atoms, and theneoalkanoyl moiety is of 7 to 14 carbon atoms, preferably 9 to 11 or 9to 13, and more preferably, about 10 or about 13, e.g., N-lower alkylneodecanamide and N-lower alkyl neotridecanamide. At present the mostpreferred of such compounds for employment as insect repellents,especially effective against German cockroaches, are methylneodecanamide and methyl neotridecanamide. Within the invention aredetergent compositions (both particulate and liquid), carpet andupholstery shampoos, human hair shampoos, hard surface cleaners, andsoap and detergent bars comprising such N-alkyl neoalkanamide(s). Alsouseful are solutions and dispersions of the neoalkanamide(s) in liquidmedia or the neoalkanamides dispersed in a particulate or powderedcarrier, which particulate or liquid products are suitable forapplication to a location from which insects are to be repelled. Alsoincluded in the invention are processes for repelling insects byapplications of insect repelling amounts of neoalkanamides of thisinvention to or near a surface, area, location or item from which suchinsects are to be repelled. In some situations the present repellentsmay be used in conjunction with insecticides, to repel the insects fromone area and toward the location of the insecticide. Alternatively, theymay be formulated with insecticides so that after the repellent effectis lost the treated area will still not be safe for insects.

Computer and manual searches of the prior art have not resulted in thefinding of any reports of volatile primary or secondary amides, likethose of this invention, that were recognized to be useful as insectrepellents. Such searches indicated that the N-lower alkylneoalkanamides of the present invention are novel and unobvious. Theclosest compounds to the N-lower alkyl neoalkanamides of this inventionappear to be those described in U.S. Pat. Nos. 4,682,982 and 4,715,862,of Steltenkamp and Camara, and in allowed U.S. patent application Ser.No. 07/071,305, of Steltenkamp, all of which are hereby incorporated byreference. However, the neoalkanamides described in the patents areemployed as antistatic agents, not as insect repellents. In Ser. No.06/894,983, of Steltenkamp and Eaton, the present N-lower alkylneoalkanamides are utilized as components of perfumes.

The N-lower alkyl secondary neoalkanamides of this invention includethose wherein the alkyl is of 1 to 18 carbon atoms, but preferably suchalkyl will be of 1 to 4 carbon atoms, more preferably one or two carbonatoms (methyl or ethyl) and most preferably such will be methyl. Theneoalkanoyl moiety, which may be derived from any of the suitableneoalkanoic acids, several of which are available commercially, willnormally be of 7 to 14 carbon atoms (of a number of carbon atoms in therange of 7 to 14), such as neodecanoyl or neoheptanoyl, and willpreferably be neodecanoyl or neotridecanoyl. Among the availableneoalkanoic acids are neopentanoic acid, neoheptanoic acid, neononanoicacid, neodecanoic acid, neododecanoic acid, neotridecanoic acid, andneotetradecanoic acid, and the corresponding alkyl neoalkanamidesthereof, such as the methyl and ethyl neoalkanamides, may be made fromsuch neoalkanoic acids. Usually the alkyl groups are straight chain butthey can also branch. Pure neoalkanamides of the types described may bemade but often the commercial or technical grade acids, which may beused, and the amides made from them, will be mixtures.

The invented amides are of the formula ##STR1## wherein R, R' and R" arealkyl groups, the sum of the carbon atom contents of which is in therange of 5 to 12, and R"' is an alkyl, preferably a lower alkyl group,more preferably of 1 to 4 carbon atoms. Further details with respect toR, R' and R" will be given later, in conjunction with a description ofneoalkanoic acids which may be employed as starting materials for theproduction of the neoalkanamides.

Infrared absorption spectra for some representative and preferredN-lower alkyl neoalkanamides of this invention are shown in the drawing,in which:

FIG. 1 is an infrared absorption spectrograph of a sample of methylneodecanamide;

FIG. 2 is an infrared spectrograph of a sample of ethyl neodecanamide;

FIG. 3 is an infrared spectrograph of a sample of methyl neoheptanamide;and

FIG. 4 is an infrared spectrograph of a sample of ethyl neoheptanamide.

Also shown in the drawing, in FIG. 5, is a plot of insect repellingaction vs. time, with the repellent effects of N-methyl neodecanamideand "DEET", a leading insect repellent, being compared.

To make the neoalkanamides of this invention neoalkanoyl chloridereactant is slowly reacted with the appropriate primary amine, in ethylether, after which reaction the reaction mixture is washed withdistilled water, dilute hydrochloric acid solution, dilute sodiumhydroxide solution, and more distilled water, until it is neutral to pHpaper. The ether is then removed by means of a steam bath, followed byemployment of a vacuum evaporator. The reaction product obtained iswater white to light amber in color and is essentially pure. In analternative method, the neoalkanoic acid may be reacted directly withthe lower alkylamine.

Neoalkanoic acids, such as neodecanoic acid, neoheptanoic acid andneopentanoic acid, are available from Exxon Chemical Americas, whichsynthesizes them by reacting a suitable branched alkene, such as abranched nonene feedstock and carbon monoxide under high pressure atelevated temperature in the presence of aqueous acidic catalyst (Kochreaction). The general mechanism involved includes generation ofcarbonium ion, followed by complexation with carbon monoxide and thecatalyst to form a "complex", which is subsequently hydrolyzed togenerate free acid. The formula of the free acid is ##STR2## Inneodecanoic acid, for example, the total number of carbon atoms in R, R'and R" is 8, 31% of the neodecanoic acid is of a structure wherein R'and R" are both methyl and R is hexyl, 67% is of a formula wherein R' ismethyl, R" is alkyl of a carbon atoms content greater than that ofmethyl and less than that of R, and R is of a carbon atoms content lessthan that of hexyl and greater than that of R", and 2% is of the formulawherein R' and R" are both of a carbon atoms content greater than thatof methyl and less than that of R, and R is of a carbon atoms contentless than that of hexyl and greater than those of R' and R". Among otherneoalkanoic acids that are available and useful to make the presentamides may be mentioned others in the 7 to 16 carbon atoms contentrange, such as neoheptanoic, neononanoic, neodecanoic, neododecanoic,neotridecanoic and neotetradecanoic acids. In the various neoalkanoicacids mentioned, when R is alkyl of 5 or more carbon atoms, such alkylis branched. Some of the neoalkanoic acids mentioned herein and methodsfor manufacturing them are described in a bulletin entitled NeoAcidsProperties, Chemistry and Applications (copyright 1982), by ExxonChemical Americas, hereby incorporated by reference.

The acyl chloride starting materials for the reactions to produce theinvented N-lower alkyl neoalkanamides may be made from the neoalkanoicacids and suitable chlorinating agents, such as phosphorus trichloride,and are available from the Lucidol Division of Pennwalt, Inc. and fromWhite Chemical Corp.

Although it is possible for the insect repellents of this invention tobe incorporated in various materials when such materials are beingmanufactured, as by being mixed in with pulp for making paper, rubberand synthetic organic polymeric plastic batches, and chips for themanufacture of pressed boards, and while the invented insect repellentsmay also be injected or otherwise inserted into the bodies of items tobe made insect repellent, usually the insect repellents will be appliedto surfaces of areas, structures or items to be made insect repellent,either by direct application of the insect repelling N-alkylneoalkanamide, in liquid solution or dispersion, or dispersed in apowdered carrier, or in a detergent composition, such as a laundrydetergent, floor or wall cleaner, upholstery or rug shampoo, hairshampoo, liquid soap, bar soap, or in any other appropriate compositionin which it may be usefully incorporated. Among such other appropriatecompositions may be mentioned insecticidal and antibacterial washes ordips for humans, pets and farm animals, furniture polishes and finishes,floor waxes and finishes, ointments, salves and topical medicaments,insecticides, fungicides, bactericides, plant fertilizers, mulches andplant potting preparations, to name only a few. In some instances meanswill be provided for recharging such items and compositions with theactive alkanamide component to renew their repellent effects. In themajority of instances the invented compositions will be applied directlyor indirectly by external application to surfaces to be treated, andafterward such application will be made on a continuing basis tomaintain a satisfactory degree of insect repellency. Thus, the insectrepellent N-alkyl neoalkanamide, such as N-methyl neodecanamide, may bepainted onto a surface to be treated or it may be applied to such asurface by washing it with a detergent composition containing the activeinsect repellent. The invented compounds are in liquid state or pastycondition at normal ambient temperatures and are water insoluble, sothey tend to be satisfactorily substantive to surfaces from detergentcompositions and from other preparations, even when such compositionsare rinsed off, and normally, after either direct or indirectapplication to such surfaces, a sufficient amount of the alkanamide willremain to be effectively insect repelling. While different applicationrates of the different alkanamides of this invention are desirably usedfor effective repelling of different insects from different surfacesunder different conditions, it is generally considered that insectrepellent effects are obtainable at surface concentrations of the activeingredient in the range of 0.002 to 100 g./sq. m. For economic reasonsand for effectiveness against more insects there will normally beapplied 0.1 or 0.2 to 10 g./sq. m., preferably 0.5 to 2 g./sq. m., e.g.,1 g./sq. m., when roach repellency is desired. Higher application rates,such as 10 to 100 g./sq. m., will often be used against mosquitoes.

Because the present insect repellents are volatile their presence can bedetected in the air near a surface to which they have been applied.Therefore, not only are the surfaces repellent to insects, which willavoid having their body parts contact such surfaces, but the vapors fromthe N-lower alkyl neoalkanamides will tend to repel insects from thesurrounding space. Thus, the application of the volatile repellent towalls of a china closet can repel roaches from the closet interior,thereby preventing them from contacting, soiling and contaminatingcontained dishes, utensils and silverware. Similarly, coating of pantrysurfaces, interior and/or exterior, with a furniture polish containingan invented volatile repellent, or use of shelf paper containing arepellent neoalkanamide can discourage roaches from entering the pantryand contaminating foods contained therein. Also, washing of clothingwith detergent compositions containing the invented repellents mayprevent insects from lighting on the clothing and its wearer, and fromstinging or biting the wearer. Shampooing of a rug with a rug shampoo orcarpet cleaner containing the invented repellent will discourage insectsfrom entering the room and from nesting and laying their eggs in orunder the rug. Washing of floors and walls with insect repellentdetergent compositions formulated for such purpose will deposit thereona substantive coating of the invented insect repellent and willdiscourage insects from contacting the floor and wall surfaces and fromentering the treated rooms. It is an important feature of the inventedinsect repellents that although they are sufficiently volatile to beeffective, their repellent properties are persistent, often lasting aslong as three weeks or more (even longer if incorporated interiorly in aproduct). The invented repellents may be formulated with insecticides,such as by being sprayed onto the surfaces of insecticidal powders,e.g., boric acid powder, which is effective against roaches. By use ofthe neoalkanamide-boric acid composition immediate effectiveness inrepelling the roaches is obtained and subsequently, after the repellentactivity may have diminished, due to exhaustion by volatilization, anyroaches that return to the area will be killed by the insecticide. It isrecognized that a more normal practice is to incorporate an attractantwith the insecticide but repellent-insecticide compositions also haveutility.

It is apparent from the foregoing brief description that the inventedinsect repellents can be used in many compositions and can be applied indiverse ways. However, among the most useful products which canincorporate the invented neoalkanamides are detergent compositions, fromwhich the neoalkanamides are surprisingly substantive to the surfaces ofwashed items. Such detergent compositions operate in several ways tocounter insect contamination of the washed item. They remove any earliercontamination, remove stains and soils, on which the insects might feed,and which could attract them, and leave behind the insect repellingneoalkanamide.

The primary component of the present detergent compositions, other thanthe insect repelling neoalkanamide, is an organic detergent material.Such material may be one of the soaps, preferably a sodium and/orpotassium higher (C₁₀₋₁₈) fatty acid soap, but is preferably a syntheticorganic detergent, which may be of the anionic, nonionic, amphoteric,ampholytic, zwitterionic or cationic type, or may be a mixture of two ormore detergents within one or more of such classifications. Preferably,the detergent will be a synthetic organic detergent of the anionic ornonionic type and often the anionic detergents will be most preferred.Descriptions of many such detergents are found in the text SurfaceActive Agents and Detergents, Vol. II, pages 25-138, by Schwartz, Perryand Berch, published in 1958 by Interscience Publishers, Inc. Suchcompounds are also described in a 1973 publication by John W.McCutcheon, entitled Detergents and Emulsifiers. Both such publicationsare hereby incorporated by reference.

The anionic detergents employed may be any such suitable detergents (orsoaps), but normally will be salts of alkali metals, such as sodium orpotassium or ammonium or lower alkanolammonium salts, e.g.,triethanolamine salts. The anionic detergent may be a sulfate,sulfonate, phosphate or phosphonate or salt of other suitable acid butusually will be a sulfate or sulfonate, which may be designated as"sulf(on)ate". The anionic detergents will include a lipophilic group,which will normally have from 10 to 18 carbon atoms, preferably inlinear higher alkyl arrangement, but other lipophilic groups may bepresent instead, preferably including 12 to 16 carbon atoms, such asbranched chain alkyl benzene. In some cases the anionic detergents mayinclude poly-lower alkoxy groups, as in ethoxylated higher fatty alcoholsulfates, e.g., triethoxylated lauryl alcohol sulfate. Normally thenumber of ethoxy groups in such detergents will be in the range of 1 to30, preferably 1 to 10. As examples of suitable anionic detergents theremay be mentioned: higher fatty alcohol sulfonates, such as sodiumtridecyl sulfonate; sodium linear alkyl benzene sulfonates, e.g., sodiumlinear tridecylbenzene sulfonate; olefin sulfonates; and paraffinsulfonates. All of the anionic detergents will preferably be sodiumsalts for most of the particulate detergent compositions of thisinvention but potassium, ammonium and triethanolammonium salts may bemore desirable for some liquid compositions. Usually the detergent willpreferably include a lipophilic alkyl moiety of 12 to 16 carbon atoms,often preferably of or averaging 12 to 13 carbon atoms.

The suitable nonionic detergents will normally be condensation productsof lipophilic compounds or moieties and lower alkylene oxides orpolyalkoxy moieties. Highly preferable lipophiles are higher fattyalcohols of 10 to 18 carbon atoms but alkyl phenols, such as octyl andnonyl phenols, may also be used. The alkylene oxide of preference isethylene oxide and normally from 3 to 30 moles of ethylene oxide will bepresent per mole of lipophile.

In preferred embodiments of the invented detergent products, the builtdetergent compositions, in which builders are employed to improve thedetergency of the synthetic organic detergent(or soap), there will bepresent a building proportion of a suitable builder. Builders used maybe inorganic or organic, water soluble or water insoluble. Among suchclasses of builders may be mentioned water soluble inorganic salts,including: polyphosphates, e.g., sodium tripolyphosphate; carbonates,e.g., sodium carbonate; bicarbonates, e.g., sodium bicarbonates;borates, e.g., borax; and silicates, e.g., sodium silicate; waterinsoluble inorganic builders, including zeolites, e.g., hydrated Zeolite4A; and water soluble organic builders, including citrates, gluconates,NTA, and polyacetal carboxylates. In some cases, as when mildness of theproduct to the human body or to delicate fabrics is important, alkalinebuilders and other "harsh" builders will be avoided, and in some casesno builders will be present at all.

Various adjuvants may be present in the detergent compositions of thisinvention to improve various characteristics of such products. Thus, forexample, bentonite may be employed as a fabric softener, perfumes andcolorants may be added for their aesthetic effects, soilanti-redeposition agents may be employed, such as sodium carboxymethylcellulose, and solvents or co-solvents may be present, as in liquidcompositions. Among other adjuvants there may be mentioned fluorescentbrighteners, antistatic agents, antibacterial agents, fungicides,foaming agents, anti-foams, flow promoters, suspending agents,antioxidants, anti-gelling agents, soil release promoting agents, andenzymes.

The detergent compositions of this invention may be in particulate,powder, tablet, bar, liquid, paste, gel, capsule, leaf, foam or"aerosol" or other suitable form, as may be best suited for the purposeintended. Methods for manufacturing products in such forms are wellknown in the art of processing soaps and detergents, and need not befurther mentioned here.

While it is possible to apply the present insect repelling N-lower alkylneoalkanamides directly to surfaces and items to be made insectrepellent, it is often more convenient and also more efficacious toutilize the repellent neoalkanamide as a liquid solution, emulsion ordispersion, or as a particulate or powder product. To make suchsolutions the neoalkanamide may be dissolved in any suitable solvent,such as a lower alcohol, e.g., ethanol, or in an aqueous alcoholicmedium. Of course, other solvents may also be employed, such ashydrocarbons, esters, ketones, aldehydes and halogenated hydrocarbons.Among the hydrocarbons and halogenated hydrocarbons there may bementioned isobutane and the chlorofluorinated lower hydrocarbons, suchas dichlorodifluoromethane, monofluorotrichloromethane and otherchlorofluoromethanes, -ethanes and -propanes. Such compounds include theliquefiable gases, which can be maintained in liquid state inpressurized dispensing containers, for ready application as sprays or inother suitable forms to locations which are to be made insect repellent.The neoalkanamides may also be in aqueous or other emulsion form, when asuitable emulisifier, hydrotrope or surface active agent is utilized,too. The invented neoalkanamides may also be dispersed in particulate orpowdered inert or active materials. Among such inert materials may bementioned silica, calcium carbonate, clay, expanded polystyrene, woodchips and sawdust. Also, the neoalkanamides may be dispersed in activematerials, such as detergent composition beads, bentonite (a fabricsoftener) and boric acid (a roach poison).

Other modes of use of the invented insect repellents, some of which havealready been mentioned, include incorporation in materials which areintended for use at or near sites from which the insects are to beexcluded. Thus, the repellents may be incorporated in shelf papers,wallpapers, wallpaper glues, rugs and carpeting, and carpet padding.They may be formulated in floor waxes, furniture polishes and otherpreparations that are intended for applications to surfaces in the areasto be treated. They may be automatically dispensed in certain areas,such as storerooms and warehouses, by timer-operated sprayers or otherdispensers, and they may be renewably charged to containers, from whichthey may be vaporized, such as absorbers and other holders, as in theunder sides of garbage can covers.

The detergent compositions of this invention, including those that areuseful for washing hard surfaces, such as floors, and also softsurfaces, such as those of carpets, laundry, and human hair, willinclude an insect repelling proportion of N-alkyl neoalkanamide or amixture of such neoalkanamides, which proportion is sufficient so thatenough of the neoalkanamide is retained on the washed surface, afterwashing of it with the detergent composition, to repel insects from suchsurface, and will also include a detersive proportion of soap orsynthetic organic detergent (or any suitable mixture thereof). Theneoalkanamide is preferably one wherein the lower alkyl is of 1 to 4carbon atoms (and that designation includes mixed lower alkyls, too,averaging such numbers of carbon atoms), more preferably being methyl orethyl, and usually most preferably being methyl. The neoalkanoyl moietyof the neoalkanamide is of 7 to 14 carbon atoms, preferably 9 to 11carbon atoms, and most preferably is of 10 or 13 carbon atoms. Mixturesof such neoalkanoyl moieties and "average" moieties, averaging withinsuch ranges or averaging 10 or 13 carbon atoms may also be used and areto be considered as being within such descriptions. As was previouslyindicated, the more preferred neodecanamides are N-methyl- and N-ethylneodecanamides, of which N-methyl neodecanamide is most preferred, inmost instances.

In particulate built laundry detergent compositions of the invention theactive detergent component will usually be synthetic organic detergentselected from the group consisting of anionic, nonionic, amphoteric,ampholytic, and zwitterionic detergents and mixtures thereof, and thebuilder will be water soluble inorganic or organic builder or waterinsoluble inorganic builder. The proportions of synthetic organicdetergent(s), builder(s), and neoalkanamide(s) to make an effectiveinsect repellent particulate synthetic organic detergent compositionwill be 1 or 5 to 35%, 10 to 90%, and 0.2 to 10%, respectively.Preferred compositions of such type will have the synthetic organicdetergent selected from the group consisting of anionic and nonionicdetergents, and mixtures thereof, may contain water soluble fillersalts(s), such as sodium sulfate, and will contain a methyl- or ethylneodecanamide, or a mixture thereof. The proportions of such componentsfor best effects in such detergent compositions will often be 7 to 30%of the synthetic organic detergent(s), 20 to 75% of the builder salt(s),0 to 50% of the filler salt(s), and 0.5 to 5% of the neoalkanamide(s).

When liquid detergents containing the invented insect repellentneoalkanamide(s) are made, the same components may be used, plus aliquid medium, but the detergent will preferably be non-soap. Sometimesa conventional emulsifying agent, such as an Emcol®, sold by WitcoChemical Co., Inc., will be employed, in emulsifying proportion. Also,hydrotropes, such as sodium toluene sulfate, and other functional andaesthetic adjuvants, such as have been employed in liquid detergentcompositions, and/or fillers, may be included, or not. In the builtliquid detergents the synthetic organic detergent content will be in therange of 2 to 25%, the builder content will be 5 to 40%, theneoalkanamide content will be 0.2 to 10%, and the liquid medium content,preferably aqueous, will be 40 to 90%. More preferably, the built liquiddetergent compositions of the invention will comprise 3 to 20% of asynthetic organic detergent which is anionic and/or nonionic, 10 to 30%of builder salt(s) for such detergent(s), which may be water soluble,such as potassium pyrophosphate, sodium carbonate, or sodium polyacetalcarboxylate, and/or water insoluble, such as sodium zeolite, 0 to 20% ofwater soluble filler salt, such as sodium sulfate, 0.5 to 5% of N-methylneodecanamide and/or N-ethyl neodecanamide, or other suitableneoalkanamide, and 50 to 90% of water, preferably deionized water.

When an insect repelling shampoo for use on upholstery, rugs and carpetsis to be made, it may comprise 1 to 35%, preferably 5 to 20%, of adetergent selected from the group consisting of water soluble soap(s)and synthetic organic detergents, 0 to 40% of builder(s) for the soapand/or detergent, often preferably 0%, and 0.2 to 10% of N-lower alkylneoalkanamide, preferably 0.5 to 5%, all being of the broad typespreviously mentioned, in a liquid medium, preferably aqueous, thepercentage of which may be in the range of 40 to 90%, preferably 70 to90%, with water being 50 to 90% of the composition, preferably 70 to90%. Alternatively, the shampoo may be in gel, paste or powder form.

When the present insect repellents are used in shampoos intended forwashing human hair on the head and for making the hair repellent ofinsects, the shampoos will preferably comprise 2 to 25% of soap and/orthe previously described synthetic organic detergent(s), and 0.2 to 10%of N-lower alkyl neoalkanamide, of the type previously discussed inconjunction with the broad description of detergent compositions, in anaqueous medium such as 40 to 90% of water, preferably deionized water.The aqueous medium may include up to half thereof of a co-solvent, suchas a lower alkanol, e.g., ethanol, or a glycol but normally thepercentage of such co-solvent will be limited to 5 to 20% of the finalproduct. In more preferred embodiments of the shampoos for human hair,there will be present 5 to 22% of synthetic organic detergent, 0 to 20%of water soluble filler salt, 0.5 to 5% of N-lower alkyl neodecanamideor mixture thereof, preferably N-methyl neodecanamide or N-ethylneodecanamide, and 50 to 90% of water, preferably deionized.

Solid or bar or cake insect repellent detergent products can also bemade, which may be used for washing persons, animals, laundry, rugs,and/or hard surfaces, such as walls and floors, to make them insectrepellent. Such products can comprise neoalkanamide repellent with soapand/or synthetic organic detergent, or may also include builders,fillers and other adjuvants, previously referred to herein. Theproportion of N-alkyl neoalkanamide in such products will normally befrom 0.2 to 10%, and that of the detersive material will be from 15 to95%. Such bars will normally be of a moisture content in the range of 2to 20% and the balance will be of builder(s) and/or filler(s) and/oradjuvant(s), when such are present. Normally, the adjuvant(s) content ofthe various detergent products will be in the range of 0.5 to 20%,total, with individual adjuvants being 0.1 to 5% for the most part.

The various detergent compositions described above may be prepared byprocesses that are well known in the art and need not be described atlength herein. Such processes include spray drying, dry mixing, sprayapplying and/or coating, sequential dissolving and/or dispersing and/oremulsifying, milling, plodding and pressing.

When the insect repellent is to be sprayed or applied in a carrier, suchas a liquid or particulate material or medium, the concentration of ittherein will be an insect repellent proportion, so that when appliedonto a surface of a material to be treated (or into the interior orother portion thereof), by spraying, dusting, rubbing, wiping, pouring,depositing, or other mechanism, the repellent applied will be in suchquantity and/or concentration that it will be effective in repellinginsects or a particular type of insect, so that such insect(s) will stayaway from the treated location. Such repelling is due to the insectbeing reluctant to contact the repellent and also in some measure is dueto the repellent effect of the vapor from the repellent, which is atleast partially volatile, although it may last for as long as two weeksor more, as normally applied, using the application concentrations thatwere previously given. Also, the repellent lasting power is increasedwhen it is incorporated in the body of an article, such as in a mattressor absorbent sponge, rather than only on a surface that is exposed tothe air.

The concentration of the repellent chemical(s) in a liquid medium, suchas an aqueous medium, in which a dispersing agent or emulsifier may beemployed, too, will usually be in the range of 0.2 to 10, 25 or 50%, butis often preferably in the range of 0.5 to 10%, e.g., about 1% or 5%,for roach repellency. The liquid medium may be water, lower alkanol,such as ethanol, lower ketone, such as acetone, lower hydrocarbon, suchas isobutane, cyclopropane or mixture thereof, or halogenated lowerhydrocarbon, such as chlorofluorinated, fluorinated or chlorinated lowerhydrocarbons, e.g., Propellants 11 and 12. The various "lower" compoundsare of 1 to 4 carbon atoms per molecule, preferably 1 or 2 carbon atoms,and in the case of those that are normally in the gaseous state, theyare under sufficient pressure to maintain them in liquid state.

Similar concentrations of the invented repellents may be employed inpowdered or particulate carriers. Thus, the invented neoalkanamides maybe applied as by spraying of liquid droplets onto powdered calciumcarbonate, silica, clay or boric acid, onto grains of such materials, oronto detergent composition particles or synthetic organic polymer beads(preferably of particle sizes between 125 microns and 2.4 mm. indiameters), in concentrations in the range of 0.2 to 10 or 25%,preferably 0.5 to 5 or 10%, for roach repellents.

In insect repelling processes or treatments in which the inventedrepellents are employed they will normally be applied to surfaces to betreated at concentrations such that 0.002 to 100 g./sq. m. initiallyremain on such surfaces after treatment, with such application ratepreferably being 0.1 or 0.2 to 5 or 10 g./sq. m. and more preferably 0.5to 2 g./sq. m., e.g., 1 g./sq. m. for action against roaches.Concentrations outside such ranges may sometimes also be of at leastpartial effectiveness. When the repellent is in a detergent compositionwhich is employed in an aqueous washing medium, such as water, the washwater will usually contain from 0.05 to 5% of the detergent compositionbut in some applications, such as shampooing of human hair or of carpetsor rugs with foam preparations, the concentration may be greater,sometimes being as high as 25%.

When the repellents are incorporated in and applied to surfaces in othermedia or preparations, such as waxes or furniture polishes, theconcentrations thereof will usually be in the same ranges as fordetergent compositions, but may be increased, if desired, in some suchinstances to as high as 25%.

The invented repellents possess various significant advantages overvarious other repellent materials available. They are essentiallynon-toxic and therefore are not hazardous to children or pets that mightcome into contact with them, after application. They are pleasantlyaromatic (sometimes fruity, with N-methyl neodecanamide and N-ethylneodecanamide resembling apples and pears in odor) and therefore do notusually adversely affect the aromas of preparations into which they areformulated. In fact, they may be useful in giving such preparationsacceptable aromas, and thereby permit the omissions of expensiveperfumes from such products. They are substantially colorless andtherefore can be employed in detergents, shampoos, polishes, sprays, andvarious compositions and preparations wherein the imparting of colorwould not be acceptable. They are effective both as contact and vaporrepellents and are superior in repelling action to various commercialinsect repellents, especially against German cockroaches, which areconsidered to be the most difficult household insect pest to control.The present repellents are long lasting, with tests having shown some ofthem, especially N-methyl neodecanamide, to be effective to repelroaches for two weeks and more after topical application. AgainstAnopheles quadrimaculatus N-methyl neodecanamide is effective for fiveweeks, by Dep't. of Agriculture screening tests (a week longer thanDEET). Against Aedes aegypti the neoalkanamide is almost as effective asDEET, using the same test. The N-alkyl neoalkanamides are sufficientlystable to be able to maintain their insect repelling properties despitebeing incorporated in various soap, detergents, polish, wax,insecticide, cosmetic, and coating preparations, in liquid, paste, gel,foam, powder, particulate or solid bar form, or in aqueous or othersolvent solutions, emulsions or dispersions, and they are highlysubstantive from such media.

Experimental work to date has proven conclusively that members of theclass of N-alkyl neoalkanamides, wherein the alkyl is lower alkyl andthe neoalkanoyl moiety is 7 to 14 carbon atoms, are superior insectrepellents, being especially effective against the common householdpest, the German cockroach, and evaluations of such compounds indicatethat they will also be effective repellents against other insects, suchas those in the group of flies, fleas, lice, mosquitoes, bees, wasps,hornets, ants and beetles, and they may also be effective againstarachnids, such as spiders, ticks and mites. Because data are mostcomplete and are very convincing for the use of N-methyl neodecanamideagainst German cockroaches, and because such data were obtained fromcontrolled tests, conducted in connection with entomological research ata major university, such data, together with some mosquito repellencydata, will be that presented in the following working examples.

The following examples illustrate but do not limit the invention. Unlessotherwise stated, all parts are by weight and all temperatures are in°C.

EXAMPLE 1

N-methyl neodecanamide was made from methyl amine and neodecanoylchloride in a reaction conducted in a 3-necked glass one-liter flaskequipped with a Chesapeake stirrer, a thermometer, an addition funnel (adropping funnel) and a condenser equipped with a Drierite® desiccanttube. The flask was placed in an ice bath and was charged with 31 gramsof methyl amine, 700 ml. of diethyl ether and 59 grams of triethyl amine(which functioned to remove from the reaction mixture any HCl that wasproduced). Then 190.5 grams of neodecanoyl chloride (obtained fromPennwalt's Lucidol Div.) were added dropwise to the flask over a periodof one hour. After completion of the addition of the neodecanoylchloride the reaction mixture was allowed to come to room temperature.The reaction mixture was then transferred to a 2-liter separatory funneland was washed twice with deionized water to separate the N-methylneodecanamide from the triethylamine chloride, once with 5% aqueoushydrochloric acid, and once with 5% aqueous sodium hydroxide, afterwhich it was further washed with distilled water until the washings wereneutral to litmus paper. The ether was then removed from the mixture byheating it on a steam bath, followed by finishing such removal with arotary vacuum evaporator. The reaction product resulting, in essentiallystoichiometric yield, is N-methyl neodecanamide. It was distilled at235° C. under 760 mm. Hg. The result is a pure, water white product. Aninfrared spectrograph of the product is shown in FIG. 1.

In similar manners there were made N-ethyl neodecanamide, N-methylneoheptanamide, N-ethyl neoheptanamide, N-methyl neotridecanamide andN-ethyl neotridecanamide, using gram-molar weights of the appropriatealkyl amines and neoalkanoyl chlorides. The same volume of diethyl ether(700 ml.) is employed as in the preparation of the N-methylneodecanamide, the same equipment is used, and the same procedures ofaddition, reaction, separation, washing, evaporation and distillationare followed. The products are obtained in essentially stoichiometricyields. Infrared spectrographs of some of such products are shown inFIGS. 2-4.

EXAMPLE 2

The compounds for which manufacturing methods are described in Example 1are made but the starting materials which act as sources of theneoalkanoyl moieties are the corresponding neoalkanoic acids instead ofthe acid chlorides, and no triethyl amine is employed. In suchreactions, in which stoichiometric proportions of neoalkanoic acids andalkyl amines are employed, with diethyl ether as the reaction solvent, aone-liter, 3-necked flask is also used but the system is closed (toavoid loss of alkyl amine) and the flask is equipped with a heatingmantle, a magnetic stirrer, a source of nitrogen gas with means forconveying it to below the surface of the reaction mixture, and athermometer and thermostatic control to regulate the temperature of thereaction mixture, which is held at 240° C. for five hours. The reactionproducts are separated, washed and have ether removed from them in thesame manner as described in Example 1. The products resulting haveinfrared spectrographs like those of the samples of correspondingproducts of Example 1.

EXAMPLE 3

The N-methyl neodecanamide made by the process of Example 1 was testedfor cockroach repellency by dissolving one gram of it in 10 ml. ofacetone and then swabbing the inside of a Dixie® cup, having an internalsurface area of 188.5 sq. cm., with the solution so that uponevaporation of the acetone there is left behind 0.0189 g. of theN-methyl neodecanamide, evenly coating the cup interior at aconcentration of 1.0 g./m². Four equidistant openings, are cut in thedrinking end edges of the cup so that when the cup is inverted andplaced on a flat surface, it will be possible for test insects (roaches)to crawl through them and under it. An identical control cup isprepared, with the sole difference being that the same proportion ofacetone is applied to the cup and floor surface but no N-methylneodecanamide is present with it. Each cup is placed in the middle of ahalf of a medially dividable reactangular area in a box, to which thereare next added 100 cockroaches. The box top is transparent and theroaches cannot escape from the box. Initially the box is in the dark butto test the effectiveness of the repellent applied to the cup interiorthe box is illuminated with a 100 watt incandescent bulb positionedabout 50 cm. above it. Each of the roaches, seeking to hide from thelight, crawls under one of the inverted cups. It is considered that anysignificant difference in the number of roaches under the experimentaland control cups indicates repellency or attraction effected by theexperimental (because the control is essentially neutral, having nothingremaining on its surfaces). After waiting one minute after illumination,a divider is slid across the box separating the experimental and controlareas, the cups are removed or knocked over, and the roaches in eachsection are counted. The number in the control area is the percentageeffectiveness of the repellent. By this test, after two days, N-methylneodecanamide is 100% effective against the control. After two days,when N-methyl neodecanamide is compared to DEET, and to a successfulcockroach repellent, identified as MGK-874, the N-methyl neodecanamide(NMNDA) is rated to be 90% and 95% effective, respectively (9 times and19 times as effective, respectively) as the other repellents. After fivedays after application of the repellent to the surfaces mentioned, asimilar test shows the experimental NMNDA repellent to be even moreeffective and such comparative effectiveness is still exhibited after 14days. However, after 21 days neither the experimental nor thecomparative repellent is of much repellent effect so comparisons afterthat time are not considered to be significant.

FIG. 5 is a graph showing comparative effectiveness (in %) of N-methylneodecanamide and DEET in repelling roaches. The number of roacheshiding under the DEET treated cup is plotted for each of the indicateddays after the applications of the repellents. The comparativeeffectiveness of the experimental compound, NMNDA, in %, is the number(out of 100) of roaches hiding under the DEET cup.

In a variation of the described test only the inner bottom parts (theupper parts when the cups are inverted) are coated with the varioustest, control, and comparison materials, at the same concentration, 1.0g./m. The results are of the same type and order as described above forthe contact repellency tests but the absolute effectivenesses of theexperimental products are less than for the contact tests, as would beexpected, due to the lesser quantities of repellents applied and thefacts that the repellents were not on the lower and side surfaces of thecups, which the roaches are more prone to occupy, so that repellentaction is more due to a vapor effect than to contact.

In the described tests results are the same whether the repellents aremade by the direct condensation method, from neoalkanoic acids, or fromthe neoalkanoyl chlorides. Similar results are obtainable when otherneoalkanamides of the invented types are employed, such as N-ethylneodecanamide, N-butyl neodecanamide, the N-methyl- and N-ethyl-neoheptanamides, -neononanamides, neoundecanamides andneotridecanamides, and best contact and vapor repellency effects areobtained when the neoalkanamides are those which are normally in liquidstate under atmospheric conditions, and are volatile enough to have thevapors thereof detectable to insects, and repugnant to them.

Instead of applying the repellents to the test surfaces in acetonesolution they may be sprayed onto such surfaces by means of "aerosol" orpressurized sprays in 50:50 mixture of isobutane and cyclobutane or60:40 solutions of Freon 12 and Freon 11 (dichloridifluoromethane andtrichloromonofluoromethane, respectively) or in other pressureizedsolvents. Instead of applying the solutions as 11.2% solutions, byweight, as in the tests reported earlier in this example, concentrationsin the range of 2% to 30% may often be used, depending to some extent onthe solubility of the repellents in the solvent system employed, forexample 15% in the Freon system, 20% in the hydrocarbon system, 5% inethanol, and 25% in methyl ethyl ketone. Aqueous systems may also beused, preferably with emulsifiers or suitable surface active agentsbeing present to hold the repellent in homogeneous suspension ascolloidal droplets, with its concentration usually being somewhat lowerthan for the organic solvent solutions, e.g., 3%, 5% and 7%. All suchliquid systems may be applied with the aids of cloths, pads, spray cansand nozzles, or gels or pastes can also be used.

In practical tests, on actual kitchen floors, counters, drainboards andwalls, and in kitchen cabinets and dishwashers, and under refrigerators,in roach-infested apartments, significantly fewer roaches will beobserved on surfaces to which or near which the invented repellents areapplied than on control surfaces, and fewer roaches are found on thebottoms and shelves of cabinets and pantries when walls thereof aretreated with the invented repellents, especially when the repellent isN-methyl neodecanamide, indicating that the repellents arevapor-effective too, as well as contact-effective. When floors, walls,counters, sinks, cabinets, appliances, windows, doors, rugs and carpetsin a house or apartment are treated with the invented repellents, e.g.,N-methyl neodecanamide or N-ethyl neodecanamide, the incidence ofcockroach infestation is reduced, compared to control apartments whereno repellent is applied. However, because of the initial presence of thepests in the premises, control of them may take as long as a week ortwo, and sometimes can require several applications of the repellent. Insome instances the application rates are desirably increased to as highas 10 g./sq. m. but in other instances such rates may be dropped to 0.01g./sq. m. or lower. Of course, results are usually better with higherapplication rates.

EXAMPLE 4

N-Methyl neodecanamide (NMNDA), dissolved at a suitable concentration,e.g., 10%, in acetone, is applied to a cotton stocking so that 1 g./ ofthe neoalkanamide is on 280 sq. cm. of stocking. Two hours aftertreatment of the stocking (during which period the acetone volatilizesoff) the stocking is pulled over a previously installed nylon stockingon the arm of a human test subject and that so-covered arm is exposed ina cage of adult mosquitoes of a type against which DEET is an effectiverepellent. Two such species are Aedes aegypti and Anophelesquadrimaculatus. If fewer than five mosquitoes bite the subject throughthe stocking during a one-minute exposure the test is repeated 24 hourslater, and if fewer than five mosquitoes then bite the subject the testis repeated weekly thereafter until five bites are received within aone-minute exposure period. The degree of repellency of a treatmentchemical or composition is measured by the number of days fromapplication of the chemical to the stocking until five mosquitoes bitethe test arm within the one-minute exposure period.

In the described test against Aedes aegypti DEET is rated 22 and NMNDAis rated 15, and when the test mosquito is Anopheles quadrimaculatus theratings are 29 and 36, respectively. Thus, the present N-lower alkylneoalkanamide is about equivalent to the DEET standard in mosquitorepellency, as measured by the described Agricultural Research Service(U.S. Department of Agriculture) screening test, as employed by theirInsects Affecting Man and Animals Research Laboratory at Gainesville,Florida.

In actual use on the human body, to which it is applied dissolved in asuitable solvent, in a skin lotion or cream, or in an "aerosol" spray,the NMNDA will be about equivalent to DEET, giving at least an hour'sprotection against Aedes aegypti and Anopheles quadrimaculatus when 0.3g./ is applied to a human forearm. Similar results are obtainable withother alkyl neoalkanamides, such as N-ethyl neodecanamide, N-methylneononanamide, N-ethyl neoundecanamide, N-methyl neotridecanamide andN-ethyl neotridecanamide, and mixtures of two or more thereof.

EXAMPLE 5 (Built Particulate Detergent)

    ______________________________________                                        Component                Percent                                              ______________________________________                                        Sodium linear tridecyl benzene sulfonate                                                               20.0                                                 Sodium tripolyphosphate  40.0                                                 Sodium carbonate         10.0                                                 Sodium bicarbonate       10.0                                                 Borax                     5.0                                                 Enzyme blend (proteolytic + amylolytic in                                                               1.0                                                 powdered carrier)                                                             Sodium carboxymethylcellulose                                                                           0.5                                                 Fluorescent brightener    1.0                                                 N-methyl neodecanamide    2.0                                                 Water                    10.5                                                                          100.0                                                ______________________________________                                    

All of the components of the detergent composition except the enzymepowder and repellent are mixed together in a crutcher slurry, which isspray dried to hollow globular bead form, of particle sizes in the rangeof Nos. 10 to 100, U.S. Sieve Series. Subsequently, the enzyme powder isblended with the spray dried beads and the insect repellent, in liquidstate, is sprayed onto the mixture, while it is being tumbled, to form auniform composition.

EXAMPLE 6 (Scouring Cleanser)

    ______________________________________                                        Component               Percent                                               ______________________________________                                        Silex (finely divided silica powder)                                                                  97.5                                                  Sodium linear dodecyl benzene sulfonate                                                               2.0                                                   N-ethyl neodecanamide   0.5                                                                           100.0                                                 ______________________________________                                    

EXAMPLE 7 (Built Liquid All-Purpose Detergent)

    ______________________________________                                        Component                   Percent                                           ______________________________________                                        *Nonionic detergent         1.0                                               Sodium linear dodecyl benzene sulfonate                                                                   2.0                                               Sodium cumene sulfonate     5.0                                               Sodium carbonate            5.0                                               Sodium bicarbonate          1.0                                               Fluorescent brightener       0.02                                             Dye                          0.01                                             N-methyl neononanamide or N-methyl neodecanamide                                                          1.0                                               Water (deionized)           84.97                                                                         100.0                                             ______________________________________                                         *Condensation product of 1 mole of higher fatty alcohol mixture averaging     10 carbon atoms, with 5 moles of ethylene oxide.                         

EXAMPLE 8 (Carpet Cleaner)

    ______________________________________                                        Component                Percent                                              ______________________________________                                        Sodium salt of lauric monoethanolamide                                                                 30.0                                                 sulfosuccinate                                                                Mixed lipolytic, proteolytic and amylolytic                                                            2.0                                                  enzymes                                                                       Sodium tripolyphosphate  20.0                                                 Sodium hexametaphosphate 5.0                                                  Sodium monophosphate     3.5                                                  Sodium bicarbonate       20.0                                                 Urea                     8.0                                                  *Micro-Cel ®         10.0                                                 N-methyl neotridecanamide                                                                              1.5                                                                           100.0                                                ______________________________________                                         *Finely divided hydrated synthetic calcium silicate (JohnsManville            Products Corp.)                                                          

This product should be diluted 1:30 with water before use. One hundredgrams will suffice to clean about ten square meters of soiled carpeting.

EXAMPLE 9 (Upholstery Cleaner)

    ______________________________________                                        Component          Percent                                                    ______________________________________                                        *Sulframin OBS     10.0                                                       Aqueous ammonia (28%)                                                                            30.0                                                       Water              58.5                                                       N-methyl neodecanamide                                                                            1.5                                                                          100.0                                                      ______________________________________                                         *Linear alkylaryl sulfonic acid (Witco Chemical Corp.)                   

Before use this upholstery cleaner is mixed 1:3 by volume with Stoddardsolvent.

EXAMPLE 10 (Hair Shampoo)

    ______________________________________                                        Component             Percent                                                 ______________________________________                                        Ammonium monoglyceride sulfate                                                                      22.0                                                    Hydroxypropyl methyl cellulose                                                                      1.0                                                     Polyacrylamide        1.0                                                     N-methyl neodecanamide                                                                              1.0                                                     Deionized water       75.0                                                                          100.0                                                   ______________________________________                                    

EXAMPLE 11 (Skin Cream)

    ______________________________________                                        Component          Amount (as indicated)                                      ______________________________________                                        Yellow ceresin wax 2.0 ounces                                                 Yellow beeswax     2.0 ounces                                                 Stearic acid       2.0 ounces                                                 White petrolatum   4.0 ounces                                                 White mineral oil  8.0 fluid ounces                                           Water              6.0 fluid ounces                                           Borax              0.3 ounce                                                  Triethanolamine    0.5 fluid ounce                                            ______________________________________                                    

The ceresin, beeswax, petrolatum, stearic acid and white mineral oil aremelted together by heating to 71° C. The borax is dissolved in hot waterand the triethanolamine is added to the solution, with the temperaturebeing raised to 71° C. The aqueous solution is poured into the meltedwax mixture with stirring and stirring is continued as the mixture isremoved from the heat. When it begins to thicken there are added to it10 grams of N-methyl neodecanamide or N-methyl neotridecanamide, or 5grams of each of such neoalkanamides.

EXAMPLE 12 (Body Lotion)

    ______________________________________                                        Component           Parts                                                     ______________________________________                                        Glyceryl monostearate                                                                             50.0                                                      Oleic acid          30.0                                                      Mineral oil         15.0                                                      Lanolin             10.0                                                      Triethanolamine     12.0                                                      Sodium lauryl sulfate                                                                             10.0                                                      Preservative        10.0                                                      Water (deionized)   980.0                                                     N-ethyl neotridecanamide                                                                          12.0                                                      ______________________________________                                    

EXAMPLE 13 (Bar Soap)

    ______________________________________                                        Component            Percent                                                  ______________________________________                                        *Higher fatty acid soap                                                                            88.0                                                     N-methyl neoundecanamide                                                                           1.0                                                      Titanium dioxide     1.0                                                      Preservative (stannic chloride)                                                                    0.2                                                      Water                9.8                                                                           100.0                                                    ______________________________________                                         *80:20 tallow:coco sodium soap                                           

Instead of soap bars and cakes, soap-synthetic bars can be made bysubstituting sodium coco-monoglyceride sulfate for up to 25% of the soapcontent of the formula. Similarly, by employing a suitable plasticizerall-synthetic detergent bars can be made.

Preservative, titanium dioxide, repellent and some water are milled withthe dried soap chips (which contain about 8% water) and are plodded tobar form, after which the bars are cut to lengths and pressed to cakeshape. Laundry bars can be made by adding 20 to 40% of builder salt,such as sodium tripolyphosphate and/or sodium carbonate to the formula,usually with an increase in the moisture content to improve plasticityduring processing. Framed laundry bars and synthetic laundry bars canalso be made and the content of the insect repellent will sometimes beincreased in such bars, up to about 5%.

EXAMPLE 14 (Repellent Spray)

    ______________________________________                                        Component          Percent                                                    ______________________________________                                        *Propellant 12     45.5                                                       **Propellant 11    45.5                                                       Mineral oil         4.0                                                       N-methyl neodecanamide                                                                            5.0                                                                          100.0                                                      ______________________________________                                         *dichlorodifluoromethane                                                      **trichloromonofluoromethane                                             

The mineral oil and insect repellent are dissolved in the pressurizedpropellant mixture and such mixture is pressure filled into a dispensingcontainer equipped with a spray nozzle designed for optimum spraying ofthe repellent solution.

EXAMPLE 15 (Powdered Repellent)

    ______________________________________                                        Component          Percent                                                    ______________________________________                                        Clay, powdered     99.0                                                       N-methyl neodecanamide                                                                           1.0                                                                           100.0                                                      ______________________________________                                    

EXAMPLE 16 (Floor Wax)

    ______________________________________                                        Component              Parts                                                  ______________________________________                                        Montan based ester wax 6.0                                                    Polyethylene wax       4.0                                                    Non-oxidized microcrystalline wax                                                                    5.0                                                    Tall oil fatty acids   0.2                                                    Aqueous potassium hydroxide solution                                                                 0.5                                                    (43%)                                                                         N,N-diethylaminoethanol                                                                              1.0                                                    Methyl carbitol        1.0                                                    N-propyl neotridecanamide                                                                            2.0                                                    Water                  80.3                                                                          100.0                                                  ______________________________________                                    

EXAMPLE 17 (Aerosol Furniture Polish)

    ______________________________________                                        Component             Parts                                                   ______________________________________                                        Carnauba wax          5.0                                                     Beeswax               5.0                                                     Ceresin wax           5.0                                                     Silicone oil (DC 200) 5.0                                                     Stoddard solvent      40.0                                                    Sodium soap (75:25 tallow:coco)                                                                     2.0                                                     Water                 130.0                                                   ______________________________________                                    

A wax-silicone concentrate is made by heating the Stoddard solvent to atemperature of about 52° C. and gradually adding to it the pre-meltedwaxes and silicone oil with agitation. Concurrently, the soap isdissolved in the water at a temperature of about 90° C., after which thehot soap solution is admixed with the wax dispersion, under vigorousagitation. The mixture is then cooled rapidly to room temperature and385 parts of water, 71 parts of naphtha and 15 parts of N-methylneodecanamide are slowly added to it. 71 Parts of Propellant 12 arepressure loaded into dispensing containers after pre-loadings of thebalance of the composition.

EXAMPLE 18 (Shelf Paper)

Rolls of shelf paper are sprayed on both sides thereof with liquidN-methyl neodecanamide in volatile solvent, such as acetone, and arere-rolled after volatilization off of the solvent. The proportion ofrepellent is regulated to be 2%, although in some instances as little as0.1% may be employed. The shelf paper has a long "shelf life" prior touse because loss of the repellent by volatilization is inhibited by therolling of the paper. In a modification of this example theneoalkanamide repellent is added to the paper pulp during themanufacturing process but care must be taken not to drive off therepellent during any drying operations.

EXAMPLE 19 (Garbage Can Insect Repellent)

A 2% concentration of N-methyl neodecanamide in a sponge is made byinjecting the neodecanamide into the interior of an open celledpolyurethane foam, of flat cylindrical shape, which is inserted in anopen holder affixed to the interior of the lid of a "step-on" kitchenwaste container.

EXAMPLE 20 (Repellent-Insecticide)

    ______________________________________                                        Component          Percent                                                    ______________________________________                                        Boric acid         98.0                                                       N-methyl neodecanamide                                                                            2.0                                                                          100.0                                                      ______________________________________                                    

The various products of Examples 4-19 are all effective in repellinginsects, especially German cockroaches. However, they represent only afew of the many compositions and articles of manufacture within thepresent invention.

The invention has been described with respect to various illustrationsand embodiments thereof but is not to be limited to them because it isevident that one of skill in the art will be able to utilize substitutesand equivalents without departing from the invention.

What is claimed is:
 1. A process for repelling insects from an area,location or item which comprises applying to or near such area, locationor item an insect repelling quantity of N-alkyl neoalkanamide(s),wherein the alkyl is of 1 to 2 carbon atoms and the neoalkanoyl moietyis of 7 to 14 carbon atoms.
 2. A process according to claim 1 whereinthe alkyl of the neoalkanamide is of 1 or 2 carbon atoms and theneoalkanoyl moiety thereof is neodecanoyl.
 3. A process according toclaim 2 wherein the neoalkanamide is applied to the area, location oritem by washing such area, location or item with a detergent compositionwhich comprises a detersive proportion of soap or synthetic organicdetergent, and an insect repelling proportion of N-lower alkylneoalkanamide(s) so that the application rate of the neoalkanamide is inthe range of 0.2 to 10 g./sq. m., said insect repelling proportion ofsaid N-lower alkyl lower neoalkanamide(s) being such that sufficientneoalkanamide is retained on the washed area, location or item, afterwashing with the detergent composition, to repel insects from such area,location or item.
 4. A process according to claim 2 wherein the alkyl ofthe neoalkanamide is methyl.
 5. A process according to claim 1 whereinthe insect repelling quantity of N-alkyl neoalkanamide(s) is applied toan area from which insects are to be repelled.
 6. A process according toclaim 1 wherein the insects to be repelled are cockroaches.
 7. A processaccording to claim 6 wherein the alkyl of the N-alkyl of the N-alkylneoalkanamide(s) is methyl.
 8. A process for repelling insects from anarea, a location or an item which comprises applying to such area,location or item an insect repelling quantity of N-alkyl neoalkylneoalkanamide(s) wherein the alkyl is of 1 to 4 carbon atoms and theneoalkanamide is of the formula ##STR3## wherein R, R' and R" are alkylgroups, the sum of the carbon atom contents of which is eight, with 31%of the neodecanoyl moiety, on the basis of the neodecanoic acid, beingthat wherein R' and R" are both methyl and R is hexyl, 67% being thatwherein R' is methyl, R" is alkyl of a carbon atoms content greater thanthat of methyl and less than that of R, and R is of a carbon atomscontent less than that of hexyl and greater than that of R", and 2%being that wherein R' and R" are both of a carbon atoms content greaterthan that of methyl and less than that of R, and R is of a carbon atomscontent less than that of hexyl and greater than that of R' and R", andR"' is alkyl of 1-4 carbon atoms.
 9. A process according to claim 8wherein R"' is methyl.